Organic silicon compound and method for producing same, and polysiloxane and method for producing same

ABSTRACT

The present invention provides a novel organosilicon compound and polysiloxane which are useful as electronic materials, optical materials, coating materials, sealing materials and catalyst carriers and which can be used as additives for improving various physical properties such as flame retardancy, heat resistance, weatherability, light resistance, electric insulating property, a surface characteristic, hardness, a mechanical strength and a chemical resistance of a polymer material. That is, the present invention relates to an organosilicon compound represented by Formula (1) and polysiloxane comprising the above organosilicon compound as a monomer:

FIELD OF THE INVENTION

The present invention relates to an organosilicon compound and aproduction process for the same and to polysiloxane and a productionprocess for the same.

BACKGROUND ART

A lot of researches on silsesquioxane have so far been made, and a largenumber of reports are present. For example, according to a generalremark (non-patent document 1) issued by Baney et al., it is confirmedthat an amorphous structure which does not show a fixed structure inaddition to a ladder structure, a cage structure and an incompletelycondensed structure is present in silsesquioxane. In the presentspecification, an incompletely condensed structure means a structure inwhich at least one part of a cage structure is not closed.

Among organosilicon compounds having silanol, the following compoundscan be given as publicly known compounds.

Among compounds represented by Formula (4), the compound in which asubstituent represented by R⁴ is cyclohexyl is reported by Brown et al.(non-patent document 2); the compounds in which it is cyclopentyl andcycloheptyl are reported by Feher et al. (non-patent document 3); andthe compounds in which it is methyl, ethyl, isobutyl and cyclohexyl arereported by Lichtenhan et al. (patent document 1).

In recent years, the silsesquioxanes represented by Formula (4) havingan incompletely condensed structure are commercially available fromHybrid Plastics Inc. of U.S.A., but the kinds thereof are limited.

Among cyclic compounds represented by Formula (5), the compound in whicha substituent represented by R⁵ is cyclohexyl or phenyl is reported byBrown et al. (non-patent document 2 or non-patent document 4), and thecompound in which it is isopropyl is reported by Unno et al. (non-patentdocument 5).

Further, an organosilicon compound of a ladder structure represented byFormula (6) having silanol at an end is reported by Unno et al.(non-patent document 6).

In Formula (6), i-Pr represents isopropyl, and n is an integer of 1 to4.

However, it has not been known that present is an organosilicon compoundof a double decker structure represented by Formula (1) which hassilanol and which is provided by the present invention. Accordingly,polysiloxane obtained by using the above organosilicon compound has notbeen known as well.

Non-patent document 1: Chem. Rev. 95, 1409 (1995)

Non-patent document 2: J. Am. Chem. Soc., 87, 4313 (1965)

Non-patent document 3: Organometallics, 10, 2526 (1991)

Non-patent document 4: J. Am. Chem. Soc., 87, 4317 (1965)

Non-patent document 5: Chem. Lett., 489 (1998)

Non-patent document 6: J. Am. Chem. Soc., 124, 1574 (2002)

Non-patent document 7: Organometallics, 19, 1077 (2000)

Patent document 1: WO 01/10871

Patent document 2: JP H1-98631 A/1989

Patent document 3: JP H1-272633 A/1989

DISCLOSURE OF THE INVENTION

Because of physical properties originating in a structure thereof,silsesquioxane is expected to be applied to wide uses such as, forexample, electronic materials, optical materials, coating materials,sealing materials and catalyst carriers. However, the kind ofsilsesquioxanes which are actually commercially available and have highpracticality is very small.

As described above, a large number of reports on silsesquioxane ispresent, but an organosilicon compound of a double decker structurehaving silanol represented by Formula (1) has not so far been known.

In light of such problems of conventional techniques as described above,the present inventors have intensively repeated researches. As a resultthereof, they have found that an organosilicon compound having silanolrepresented by Formula (1) can readily be obtained at a good yield byreacting an organosilicon compound represented by Formula (2) with aproton donor. Further, they have found that useful polysiloxane isobtained by reacting the organosilicon compound having silanolrepresented by Formula (1) with an organosilicon compound having ahydrolytic group or silanol, and thus they have completed the presentinvention.

The organosilicon compound and the polysiloxane according to the presentinvention are useful as electronic materials, optical materials, coatingmaterials, sealing materials and catalyst carriers. Further, theorganosilicon compound and the polysiloxane according to the presentinvention can also be used as additives for improving various physicalproperties such as flame retardancy, heat resistance, weatherability,light resistance, electric insulating property, a surfacecharacteristic, hardness, a mechanical strength and a chemicalresistance of a polymer material.

The present invention comprises the following structures.

[1] An organosilicon compound represented by Formula (1):

wherein each R¹ is group selected independently from hydrogen, alkylhaving 1 to 45 carbon atoms in which optional hydrogen may be replacedby fluorine and in which optional —CH₂— may be replaced by —O—, —CH═CH—,cycloalkylene or cycloalkenylene, substituted or unsubstituted aryl andarylalkyl constituted of alkylene in which optional hydrogen may bereplaced by fluorine and optional —CH₂— may be replaced by —O—, —CH═CH—or cycloalkylene and substituted or unsubstituted aryl.

[2] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen and alkylhaving 1 to 30 carbon atoms in which optional hydrogen may be replacedby fluorine and optional —CH₂— may be replaced by —O— or cycloalkylene.

[3] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen, alkenylhaving 2 to 20 carbon atoms in which optional hydrogen may be replacedby fluorine and optional —CH₂— may be replaced by —O— or cycloalkyleneand alkyl having 1 to 20 carbon atoms in which optional hydrogen may bereplaced by fluorine and at least one —CH₂— is replaced bycycloalkenylene.

[4] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen, phenyl inwhich optional hydrogen may be replaced by halogen or alkyl having 1 to10 carbon atoms and naphthyl; in which in the alkyl which is asubstituent of the phenyl optional hydrogen may be replaced by fluorineand optional —CH₂— may be replaced by —O—, —CH═CH—, cycloalkylene orphenylene; and when the phenyl or the naphthyl has plural substituents,the substituents may be the same group or different groups.

[5] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen andphenylalkyl constituted of phenyl in which optional hydrogen may bereplaced by halogen or alkyl having 1 to 10 carbon atoms and alkylenehaving 1 to 12 carbon atoms; in which in the alkyl which is asubstituent of the phenyl optional hydrogen may be replaced by fluorineand optional —CH₂— may be replaced by —O—, —CH═CH—, cycloalkylene orphenylene, in the above alkylene optional hydrogen may be replaced byfluorine and optional —CH₂— may be replaced by —O— or cycloalkylene; andwhen the phenyl has plural substituents, the substituents may be thesame group or different groups.

[6] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen andphenylalkenyl constituted of phenyl in which optional hydrogen may bereplaced by halogen or alkyl having 1 to 10 carbon atoms and alkenylenehaving 2 to 12 carbon atoms; in which in the alkyl having 1 to 10 carbonatoms which is a substituent of the phenyl optional hydrogen may bereplaced by fluorine and optional —CH₂— may be replaced by —O—, —CH═CH—,cycloalkylene or phenylene, in the above alkenylene optional hydrogenmay be replaced by fluorine and optional —CH₂— may be replaced by —O— orcycloalkylene; and when the phenyl has plural substituents, thesubstituents may be the same group or different groups.

[7] The organosilicon compound as described in the above item [1],wherein each R¹ is group selected independently from hydrogen, alkylhaving 1 to 8 carbon atoms in which optional hydrogen may be replaced byfluorine and optional —CH₂— may be replaced by —O—, —CH═CH—,cycloalkylene or cycloalkenylene, phenyl in which optional hydrogen maybe replaced by halogen, methyl or methoxy, phenylalkyl constituted ofphenyl in which optional hydrogen may be replaced by fluorine, alkylhaving 1 to 4 carbon atoms, vinyl or methoxy and alkylene having 1 to 8carbon atoms in which optional —CH₂— may be replaced by —O—, —CH═CH— orcycloalkylene, and naphthyl; and when the phenyl has pluralsubstituents, the substituents may be the same group or differentgroups.

[8] The organosilicon compound as described in the above item [1],wherein all R¹ are the same group selected from hydrogen, alkyl having 1to 8 carbon atoms in which optional hydrogen may be replaced by fluorineand optional —CH₂— may be replaced by —O—, —CH═CH—, cycloalkylene orcycloalkenylene, phenyl in which optional hydrogen may be replaced byhalogen, methyl or methoxy, phenylalkyl constituted of phenyl in whichoptional hydrogen may be replaced by fluorine, alkyl having 1 to 4carbon atoms, vinyl or methoxy and alkylene having 1 to 8 carbon atomsin which optional —CH₂— may be replaced by —O—, —CH═CH— orcycloalkylene, and naphthyl; and when the phenyl has pluralsubstituents, the substituents may be the same group or differentgroups.

[9] The organosilicon compound as described in the above item [1],wherein all R¹ are the same group selected from hydrogen, phenyl inwhich optional hydrogen may be replaced by halogen, methyl or methoxy,phenylalkyl constituted of phenyl in which optional hydrogen may bereplaced by fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxyand alkylene having 1 to 8 carbon atoms in which optional —CH₂— may bereplaced by —O—, —CH═CH— or cycloalkylene, and naphthyl; and when thephenyl has plural substituents, the substituents may be the same groupor different groups.

[10] The organosilicon compound as described in the above item [1],wherein all R¹ are phenyl.

[11] A production process for the organosilicon compound as described inthe above item [1], characterized by using an organosilicon compoundrepresented by Formula (2):

wherein R² has the same meaning as that of R¹ in Formula (1) describedin the above item [1], and M is a monovalent alkaline metal atom.

[12] A production process for the organosilicon compound as described inthe above item [1], characterized by reacting the organosilicon compoundrepresented by Formula (2) with a proton donor.

[13] A production process for the organosilicon compound as described inthe above item [1], characterized by reacting the organosilicon compoundrepresented by Formula (2) with an inorganic acid.

[14] A production process for the organosilicon compound as described inthe above item [1], characterized by reacting the organosilicon compoundrepresented by Formula (2) with an organic acid.

[15] Polysiloxane represented by Formula (3):

wherein R³ has the same meaning as that of R¹ in Formula (1) describedin the above item [1], and m is an integer of 2 to 1000.

[16] The polysiloxane as described in the above item [15], wherein m isan integer of 2 to 500.

[17] The polysiloxane as described in the above item [15], wherein m isan integer of 2 to 50.

[18] Polysiloxane obtained by subjecting the organosilicon compound asdescribed in any of the above items [1] to [10] to polycondensationreaction.

[19] Polysiloxane obtained by reacting the organosilicon compound asdescribed in any of the above items [1] to [10] with an organosiliconcompound having a hydrolytic group.

[20] Polysiloxane obtained by reacting the organosilicon compound asdescribed in any of the above items [1] to [10] with an organosiliconcompound having silanol.

[21] The polysiloxane as described in the above item [19], wherein thehydrolytic group is an alkoxysilyl group.

[22] The polysiloxane as described in the above item [19], wherein thehydrolytic group is an acetoxysilyl group.

[23] The polysiloxane as described in the above item [19], wherein thehydrolytic group is a halosilyl group.

[24] The polysiloxane as described in the above item [19], wherein thehydrolytic group is an aminosilyl group.

[25] A production process for polysiloxane, characterized by subjectingthe organosilicon compound as described in any of the above items [1] to[10] to polycondensation reaction.

[26] A production process for polysiloxane, characterized by reactingthe organosilicon compound as described in any of the above items [1] to[10] with an organosilicon compound having a hydrolytic group.

[27] A production process for polysiloxane, characterized by reactingthe organosilicon compound as described in any of the above items [1] to[10] with an organosilicon compound having silanol.

[28] The production process for polysiloxane as described in the aboveitem [26], wherein the hydrolytic group is an alkoxysilyl group.

[29] The production process for polysiloxane as described in the aboveitem [26], wherein the hydrolytic group is an acetoxysilyl group.

[30] The production process for polysiloxane as described in the aboveitem [26], wherein the hydrolytic group is a halosilyl group.

[31] The production process for polysiloxane as described in the aboveitem [26], wherein the hydrolytic group is an aminosilyl group.

In the present specification, silsesquioxane shall be used as a generalterm for compounds obtained by hydrolyzing and condensing trifunctionalhydrolytic silicon compounds.

The organosilicon compound and the polysiloxane according to the presentinvention are novel compounds and expected to be used as electronicmaterials, optical materials, coating materials, sealing materials andcatalyst carriers. Also, the organosilicon compound and the polysiloxaneaccording to the present invention are expected as well to be used asadditives for improving various physical properties such as flameretardancy, heat resistance, weatherability, light resistance, electricinsulating property, a surface characteristic, hardness, a mechanicalstrength and a chemical resistance of a polymer material. Further, thepolysiloxane comprising the organosilicon compound of the presentinvention as a monomer is expected to have a high compatibility withresins.

The production process for an organosilicon compound provided by thepresent invention makes it possible to readily obtain the organosiliconcompound of the present invention at a good yield. Further, theproduction process for polysiloxane provided by the present inventionmakes it possible to readily obtain the useful polysiloxane of thepresent invention.

BEST MODE FOR CARRYING OUT THE INVENTION

In the following explanations, the organosilicon compound represented byFormula (1) shall be shown as the compound (1), and the organosiliconcompound represented by Formula (2) shall be shown as the compound (2).Compounds represented by the other formulas shall be shown in the samemanner.

Alkyls and alkylenes described in the present invention may be lineargroups or branched groups in all cases. This shall apply to a case whereoptional hydrogen is replaced by halogen or a cyclic group in the abovegroups and a case where optional —CH₂— is replaced by —O—, —CH═CH—,cycloalkylene or cycloalkenylene.

The term “optional” used in the present invention show that not only thepositions but also the numbers are optional. When plural hydrogens or—CH₂— are substituted, they each may be replaced by different groups.For example, when two —CH₂— are replaced by —O— and —CH═CH— in alkyl,alkoxyalkenyl or alkenyloxyalkyl are shown. In this case, all groups ofalkoxy and alkenylene in the alkoxyalkenyl and alkenyl and alkylene inthe alkenyloxyalkyl may be linear groups or branched groups. In thepresent invention, however, when it is described that optional —CH₂— isreplaced by —O—, adjacent plural —CH₂— are not replaced by —O—.

The organosilicon compound provided by the present invention isrepresented by the following Formula (1):

In Formula (1), each R¹ is group independently selected from the groupconsisting of hydrogen, alkyl having 1 to 45 carbon atoms, substitutedor unsubstituted aryl and substituted or unsubstituted arylalkyl. All R¹are preferably the same group but eight R¹ may be constituted of two ormore different groups.

The combinations of a case where eight R¹ are constituted of differentgroups are, for example, a case where they are constituted of two ormore alkyls, a case where they are constituted of two or more aryls, acase where they are constituted of two or more aralkyls, a case wherethey are constituted of hydrogen and at least one aryl, a case wherethey are constituted of at least one alkyl and at least one aryl, a casewhere they are constituted of at least one alkyl and at least onearalkyl and a case where they are constituted of at least one aryl andat least one aralkyl. They may be combinations other than the aboveexamples. A process for producing the compound (1) having at least twodifferent R¹ shall be described later.

When R¹ is alkyl, the number of carbon atoms is 1 to 45. The preferredcarbon number is 1 to 30. More preferred carbon number is 1 to 8.Optional hydrogen thereof may be replaced by fluorine, and optional—CH₂— thereof may be replaced by —O—, —CH═CH—, cycloalkylene orcycloalkenylene. The preferred examples of the alkyl are non-substitutedalkyl having 1 to 30 carbon atoms, alkoxyalkyl having 2 to 29 carbonatoms, a group in which one —CH₂— in alkyl having 1 to 8 carbon atoms isreplaced by cycloalkylene, alkenyl having 2 to 20 carbon atoms,alkenyloxyalkyl having 2 to 20 carbon atoms, alkyloxyalkenyl having 2 to20 carbon atoms, a group in which one —CH₂— in alkyl having 1 to 8carbon atoms is replaced by cycloalkenylene, and groups in whichoptional hydrogens in the respective groups given above are replaced byfluorine. Cycloalkylene and cycloalkenylene having 3 to 8 carbon atomsis preferred.

The examples of unsubstituted alkyl having 1 to 30 carbon atoms aremethyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl,1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl, octyl,2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,hexadecyl, octadecyl, eicosyl, docosyl and triacontyl.

The examples of fluorinated alkyl having 1 to 30 carbon atoms are3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl,tridecafluoro-1,1,2,2-tetrahydrooctyl,heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1,1,2,2-dodecyl andperfluoro-1,1,2,2-tetradecyl.

The examples of alkoxyalkyl having 2 to 29 carbon atoms are3-methoxypropyl, methoxyethoxyundecyl and 3-heptafluoroisopropoxypropyl.

The examples of a group in which one —CH₂— in alkyl having 1 to 8 carbonatoms is replaced by cycloalkylene are cyclohexylmethyl,adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl andcyclooctyl. Cyclohexyl is an example in which —CH₂— in methyl isreplaced by cyclohexylene.

Cyclohexylmethyl is an example in which —CH₂— in ethyl is replaced bycyclohexylene.

The examples of alkenyl having 2 to 20 carbon atoms are ethenyl,2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl and21-docosenyl. The example of alkenyloxyalkyl having 2 to 20 carbon atomsis allyloxyundecyl. The examples of alkyl which has 1 to 8 carbon atomsand in which one —CH₂— is replaced by cycloalkenylene are2-(3-cyclohexenyl)ethyl, 5-(bicycloheptenyl)ethyl, 2-cyclopentenyl,3-cyclohexenyl, 5-norbornene-2-yl and 4-cyclooctenyl.

The examples of a case where R¹ in Formula (1) is substituted orunsubstituted aryl are phenyl in which optional hydrogen may be replacedby halogen or alkyl having 1 to 10 carbon atoms and naphthyl. Thepreferred examples of halogen are fluorine, chlorine and bromine. In thealkyl having 1 to 10 carbon atoms, optional hydrogen may be replaced byfluorine, and optional —CH₂— may be replaced by —O—, —CH═CH— orphenylene.

That is, the preferred examples of a case where R¹ is substituted orunsubstituted aryl are phenyl, naphthyl, alkylphenyl, alkyloxyphenyl,alkenylphenyl, phenyl having as a substituent, alkyl having 1 to 10carbon atoms in which optional —CH₂— is replaced by phenylene and groupsin which optional hydrogens are replaced by halogens in the respectivegroups listed above. In the present invention, when called merelyphenyl, it means unsubstituted phenyl unless otherwise described. Thesame shall apply to naphthyl.

The examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyland 4-bromophenyl. The examples of alkylphenyl are 4-methylphenyl,4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl,4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl,2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6- triethylphenyl,4-(1-methylethyl)phenyl, 4-(1,1-dimethylethyl)phenyl,4-(2-ethylhexyl)phenyl and 2,4, 6-tris (1-methylethyl) phenyl. Theexamples of alkyloxyphenyl are 4-methoxyphenyl, 4-ethoxyphenyl,4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 4-heptyloxyphenyl,4-decyloxyphenyl, 4-octadecyloxyphenyl, 4-(1-methylethoxy)phenyl,4-(2-methylpropoxy)phenyl and 4-(1,1-dimethylethoxy)phenyl. The examplesof alkenylphenyl are 4-ethenylphenyl, 4-(1-methylethenyl)phenyl and4-(3-butenyl)phenyl.

The examples of phenyl having as a substituent, alkyl having 1 to 10carbon atoms in which optional —CH₂— is replaced by phenylene are4-(2-phenylethenyl)phenyl, 4-phenoxyphenyl, 3-phenylmethylphenyl,biphenyl and terphenyl. 4-(2-Phenylethenyl)phenyl is an example in whichone —CH₂— in ethyl of ethylphenyl is replaced by phenylene and in whichthe other —CH₂— is replaced by —CH═CH—.

The examples of phenyl in which a part of hydrogens on a benzene ring isreplaced by halogen and in which other hydrogens are replaced by alkyl,alkyloxy or alkenyl are 3-chloro-4-methylphenyl,2,5-dichloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl,2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl,3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl,3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl,3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl,3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl,2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propoxyphenyl and4-ethenyl-2,3,5,6-tetrafluorophenyl.

Next, the examples of a case where R¹ in Formula (1) is substituted orunsubstituted arylalkyl shall be given. In alkylene of the arylalkyl,optional hydrogen may be replaced by fluorine, and optional —CH₂— may bereplaced by —O—, —CH═CH— or cycloalkylene. The preferred example of thearylalkyl is phenylalkyl. In this case, the preferred carbon atom numberof the alkylene is 1 to 12, and the more preferred carbon atom number is1 to 8.

The examples of unsubstituted phenylalkyl are phenylmethyl,2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl,6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenylpropyl,1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl,1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl and1-phenylhexyl.

In the phenylalkyl, optional hydrogen on a benzene ring may be replacedby halogen or alkyl having 1 to 12 carbon atoms. In this alkyl having 1to 12 carbon atoms, optional hydrogen may be replaced by fluorine, andoptional —CH₂— may be replaced by —O—, —CH═CH—, cycloalkylene orphenylene. The examples of phenylalkyl in which optional hydrogen onphenyl is replaced by fluorine are 4-fluorophenylmethyl,2,3,4,5,6-pentafluorophenylmethyl, 2-(2,3,4,5,6-pentafluorophenyl)ethyl,3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorophenyl)propyl and2-(4-fluorophenyl)propyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl,2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl,2,3,6-trichlorophenylmethyl, 2,4,6-trichlorophenylmethyl,2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl,2,3,4,5,6-pentachlorophenylmethyl, 2-(2-chlorophenyl)ethyl,2-(4-chlorophenyl)ethyl, 2-(2,4,5-chlorophenyl)ethyl,2-(2,3,6-chlorophenyl)ethyl, 3-(3-chlorophenyl)propyl,3-(4-chlorophenyl)propyl, 3-(2,4,5-trichlorophenyl)propyl,3-(2,3,6-trichlorophenyl)propyl, 4-(2-chlorophenyl)butyl,4-(3-chlorophenyl)butyl, 4-(4-chlorophenyl)butyl,4-(2,3,6-trichlorophenyl)butyl, 4-(2,4,5-trichlorophenyl)butyl,1-(3-chlorophenyl)ethyl, 1-(4-chlorophenyl)ethyl,2-(4-chlorophenyl)propyl, 2-(2-chlorophenyl)propyl and1-(4-chlorophenyl)butyl.

The examples of phenylalkyl in which optional hydrogen on phenyl isreplaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl,2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl,2,3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl,2-(4-bromophenyl)ethyl, 3-(4-bromophenyl)propyl,3-(3-bromophenyl)propyl, 4-(4-bromophenyl)butyl, 1-(4-bromophenyl)ethyl,2-(2-bromophenyl)propyl and 2-(4-bromophenyl)propyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms are2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl,4-dodecylphenylmethyl, 3,5-dimethylphenylmethyl,2-(4-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl,2-(2,5-dimethylphenyl)ethyl, 2-(4-ethylphenyl)ethyl,2-(3-ethylphenyl)ethyl, 1-(4-methylphenyl)ethyl,1-(3-methylphenyl)ethyl, 1-(2-methylphenyl)ethyl,2-(4-methylphenyl)propyl, 2-(2-methylphenyl)propyl,2-(4-ethylphenyl)propyl, 2-(2-ethylphenyl)propyl,2-(2,3-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)propyl,2-(3,5-dimethylphenyl)-propyl, 2-(2,4-dimethylphenyl)propyl,2-(3,4-dimethylphenyl)propyl, 2-(3,5-dimethylphenyl)butyl,4-(1-methylethyl)phenylmethyl, 2-(4-(1,1-dimethylethyl)phenyl)ethyl,2-(4-(1-methylethyl)-phenyl)propyl and2-(3-(1-methylethyl)phenyl)propyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms and in which hydrogenin this alkyl is replaced by fluorine are 3-trifluoromethylphenylmethyl,2-(4-trifluoromethylphenyl)ethyl, 2-(4-nonafluorobutyl-phenyl)ethyl,2-(4-tridecafluorohexylphenyl)ethyl,2-(4-heptadecafluorooctylphenyl)ethyl, 1-(3-trifluoromethylphenyl)ethyl,1-(4-trifluoromethyl-phenyl)ethyl, 1-(4-nonafluorobutylphenyl)ethyl,1-(4-tridecafluorohexylphenyl)ethyl,1-(4-heptadecafluorooctylphenyl)ethyl,2-(4-nonafluorobutylphenyl)propyl,1-methyl-1-(4-nonafluorobutylphenyl)ethyl,2-(4-tridecafluorohexyl-phenyl)propyl,1-methyl-1-(4-tridecafluorohexyl-phenyl)ethyl,2-(4-heptadecafluorooctylphenyl)propyl and1-methyl-1-(4-heptadecafluorooctylphenyl)ethyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms and in which —CH₂— inthis alkyl is replaced by —CH═CH— are 2-(4-ethenylphenyl)ethyl,1-(4-ethenylphenyl)ethyl and 1-(2-(2-propenyl)phenyl)ethyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms and in which —CH₂— inthis alkyl is replaced by —O— are 4-methoxyphenylmethyl,3-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl,3-(4-methoxyphenyl)propyl, 3-(2-methoxyphenyl)propyl,3-(3,4-dimethoxyphenyl)propyl, 11-(4-methoxyphenyl)undecyl,1-(4-methoxyphenyl)ethyl, (3-methoxymethylphenyl)ethyl and3-(2-nonadecafluorodecenyloxyphenyl)propyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms and in which one of—CH₂— in this alkyl is replaced by cycloalkylene, to give the examplesincluding a case in which another —CH₂— is replaced by —O—, arecyclopentylphenylmethyl, cyclopentyloxyphenylmethyl,cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyland cyclohexyloxyphenylmethyl.

The examples of phenylalkyl in which optional hydrogen on a benzene ringis replaced by alkyl having 1 to 12 carbon atoms and in which one of—CH₂— in this alkyl is replaced by phenylene, to give the examplesincluding a case in which another —CH₂— is replaced by —O—, are2-(4-phenoxyphenyl)ethyl, 2-(4-phenoxyphenyl)propyl,2-(2-phenoxyphenyl)propyl, 4-biphenylylmethyl, 3-biphenylylethyl,4-biphenylylethyl, 4-biphenylylpropyl, 2-(2-biphenylyl)propyl and2-(4-biphenylyl)propyl.

The examples of phenylalkyl in which at least two hydrogens on a benzenering are replaced by different groups are3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl,3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl,5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl,2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl,2,3-dichloro-4-methyl-phenylmethyl, 2,5-dichloro-4-methylphenylmethyl,3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl,2,3,5,6-tetrachloro-4-methylphenylmethyl,2,3,4,6-tetrachloro-5-methylphenylmethyl,2,3,4,5-tetrachloro-6-methylphenylmethyl,4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl,2,4-dichloro-3,5-dimethylphenylmethyl,2,6-dichloro-3,5-dimethylphenylmethyl,2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl,4-bromo-2-methylphenylmethyl, 5-bromo-2-methylphenyl-methyl,6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl,2,3-dibromo-4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl,2,3,5,6-tetrabromo-4-methylphenylmethyl and11-(3-chloro-4-methoxyphenyl)undecyl.

The most preferred examples of phenyl in the phenylalkyl areunsubstituted phenyl and phenyl having at least one of fluorine, alkylhaving 1 to 4 carbon atoms, ethenyl and methoxy as a substituent. Theexamples of phenylalkyl in which —CH₂— in alkylene is replaced by —O—,—CH═CH— or cycloalkylene are 3-phenoxypropyl, 1-phenylethenyl,2-phenylethenyl, 3-phenyl-2-propenyl, 4-phenyl-4-pentenyl,13-phenyl-12-tridecenyl, phenylcyclohexyl and phenoxycyclohexyl. Theexamples of phenylalkenyl in which hydrogen on a benzene ring isreplaced by fluorine or methyl are 4-fluorophenylethenyl,2,3-difluorophenylethenyl, 2,3,4,5,6-pentafluorophenylethenyl and4-methylphenylethenyl.

Among the above groups, the preferred examples of R¹ are groups selectedfrom alkyl having 1 to 8 carbon atoms, substituted or unsubstitutedphenyl, substituted or unsubstituted phenylalkyl and naphthyl. The morepreferred examples of R¹ are groups selected from substituted orunsubstituted phenyl, substituted or unsubstituted phenylalkyl andnaphthyl. In this case, in the alkyl having 1 to 8 carbon atoms,optional hydrogen may be replaced by fluorine, and optional —CH₂— may bereplaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene. In thesubstituted or unsubstituted phenyl, optional hydrogen may be replacedby halogen, methyl or methoxy.

In the substituted or unsubstituted phenylalkyl, the alkylene has 1 to 8carbon atoms; optional hydrogen on a benzene ring may be replaced byfluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy; andoptional —CH₂— in the alkylene may be replaced by —O—, —CH═CH— orcycloalkylene. In the above groups, when the phenyl has pluralsubstituents, these substituents may be the same group or differentgroups. All of R¹ in Formula (1) are preferably the same group selectedfrom the above preferred examples.

The more preferred specific examples of R¹ are phenyl, halogenatedphenyl, phenyl having at least one methyl, methoxyphenyl, naphthyl,phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl,1-methyl-2-phenylethyl, pentafluorophenylpropyl, 4-ethylphenylethyl,3-ethylphenylethyl, 4-(1,1-dimethylethyl)phenylethyl,4-ethenylphenylethyl, 1-(4-ethenylphenyl)ethyl, 4-methoxyphenylpropyland phenoxypropyl. Among the above examples, phenyl is most preferred.

Next, a production process for the compound (2) shall be explained. Thecompound (2) can readily be produced at a good yield by hydrolyzing acompound (7) in an organic solvent containing an oxygen atom in amolecule under the presence of monovalent alkaline metal hydroxide andthen subjecting it to polycondensation:

In Formula (7), R⁷ is defined in the same manner as R² in Formula (2),and A¹ is a hydrolytic group. Accordingly, the most preferred examplesof R⁷ are, as described above, phenyl, halogenated phenyl, phenyl havingat least one methyl, methoxyphenyl, naphthyl, phenylmethyl, phenylethyl,phenylbutyl, 2-phenylpropyl, 1-methyl-2-phenylethyl,pentafluorophenylpropyl, 4-ethylphenylethyl, 3-ethylphenylethyl,4-(1,1-dimethylethyl)phenylethyl, 4-ethenylphenylethyl,1-(4-ethenylphenyl)ethyl, 4-methoxyphenylpropyl and phenoxypropyl. Thepreferred examples of Al are chlorine, acetoxy and alkoxy. This alkoxygroup is a group eliminated by hydrolysis, and therefore it is not someaningful to restrict the range of the number of the carbon atomthereof. However, considering the availability thereof, the number ofthe carbon atom thereof is 1 to 4.

The examples of the compound (7) are phenyltrichlorosilane,phenyltrimethoxysilane, phenyltriethoxysilane,phenyltri-n-propoxysilane, phenyltriisopropoxysilane,phenyltri-n-butoxysilane, p-tolyltrimethoxysilane,p-tolyltriethoxysilane, chlorophenyltrichlorosilane,chlorophenyltrimethoxysilane and chlorophenyltriethoxysilane.

A large part of the compounds (7) described above is commerciallyavailable. However, the compounds which are not commercially availablecan be obtained by publicly known synthetic techniques, for example, bya method in which halosilane is reacted with a Grignard reagent.

Next, the monovalent alkaline metal hydroxide used for producing thecompound (2) shall be explained. Lithium hydroxide, sodium hydroxide,potassium hydroxide and cesium hydroxide can be given as the examples ofthe monovalent alkaline metal hydroxide, and considering theavailability thereof, sodium hydroxide and potassium hydroxide arepreferred.

An addition amount of the monovalent alkaline metal hydroxide inproducing the compound (2) is 0.3 to 1.5, more preferably 0.4 to 0.8 interms of a molar ratio to the compound (7). If the molar ratio falls inthe above range, cyclic or linear low molecular weight siloxanecompounds and high molecular weight siloxane compounds are preventedfrom being formed, and the compound (2) can readily be obtained.

Next, an addition amount of water shall be explained. An addition amountof water is 1.0 to 1.5, more preferably 1.1 to 1.3 in terms of a molarratio to the compound (7). If it falls in the above range, remaining ofthe hydrolytic group, formation of low molecular weight siloxanecompounds and formation of high molecular weight siloxane compounds canbe prevented. Addition timing of water shall not specifically berestricted, and it may be mixed in advance with other raw materials ormay be added later.

Further, hydrolytic reaction of the compound (7) is carried outpreferably under the presence of an organic solvent containing an oxygenatom in a molecule. The preferred examples of the above organic solventare linear, branched or cyclic monohydric alcohols. The examples of thelinear alcohols are methanol, ethanol, 1-propanol, 1-butanol,1-pentanol, 1-hexanol, 1-heptanol and 1-octanol. The examples of thebranched alcohols are 2-propanol, 2-butanol, 2-methyl-2-propanol,2-hexanol and 3-hexanol. The examples of the cyclic alcohols arecyclopentanol, cyclohexanol and cycloheptanol.

As described above, the organic solvent is preferably used in producingthe compound (2), and the above organic solvents may be used alone orplural organic solvents may be used in a mixture. A use amount thereofshall not specifically be restricted. Factors for determining a useamount of the organic solvent are economical viewpoints such as energyefficiency and a time efficiency and a stirring efficiency. Accordingly,the use amount range which has to be strictly kept is not present, andconsidering the factors described above, it shall be 0.3 to 50 times,more preferably 5 to 40 times in terms of a volume ratio to the compound(7). It is important to adopt the optimum conditions in the range of theproduction conditions described above according to the compound (7) usedas the raw material.

The compound (2) is scarcely soluble in organic solvents, and thereforeit starts to be deposited as the reaction goes on. Time required fordeposition is varied according to the conditions such as the organicsolvent used and a use amount thereof, and it is usually several minutesto several ten hours. The compound (2) deposited can readily beseparated from the organic solvent by filtering.

However, the compound (2) obtained has a low solubility in organicsolvents, and therefore an analytical method for analyzing the structurethereof is restricted. Accordingly, if capping reaction is carried outby trimethylchlorosilane to raise the solubility thereof in organicsolvents, it shall become possible to readily carry out the structuralanalysis thereof.

If at least two compounds (7) are used in synthesizing the compound (2),the compound (2) in which eight R² in Formula (2) are constituted of atleast two different groups can be obtained.

In Formula (2), R² is defined in the same manner as R¹ in Formula (1),and M is a monovalent alkaline metal atom.

Next, a production process for the compound (1) shall be explained. Thecompound (1) can be obtained by mixing the compound (2) obtained by themethod described above, if necessary, with an organic solvent and addinga proton donor to this mixture to react them.

The organic solvent used for the above reaction shall not specificallybe restricted as long as it does not hinder the progress of thereaction. It includes, for example, aliphatic hydrocarbons such ashexane and heptane, aromatic hydrocarbons such as benzene, toluene andxylene, ethers such as diethyl ether, tetrahydrofuran and dioxane,halogenated hydrocarbons such as methylene chloride and carbontetrachloride and acetates such as methyl acetate, ethyl acetate andbutyl acetate, and tetrahydrofuran and acetates are preferred.

A preferred proportion of the compound (2) mixed with the organicsolvent falls in a range of 0.05 to 50% by weight based on the weight ofthe solvent. If it is 50% by weight or less, a concentration of theby-produced salts can be reduced, and it is advantageous for allowingthe reaction to proceed. On the other hand, if it is 0.05% by weight ormore, it is preferred in terms of the cost. The more preferredproportion falls in a range of 1 to 10% by weight.

Next, the proton donor used for the above reaction shall be explained.The proton donor is a Brønsted acid (hereinafter referred to as theacid). The above proton donor may be an inorganic acid or an organicacid and shall not specifically be restricted as long as it reacts withthe compound (2) to form the compound (1). Capable of being specificallygiven as the examples thereof are, for example, cyanic acid, isocyanicacid, thiocyanic acid, isothiocyanic acid, nitric acid, nitrous acid,sulfuric acid, sulfurous acid, carbonic acid, hydrochloric acid,hydrobromic acid, phosphoric acid, boric acid, formic acid, acetic acid,propionic acid, butyric acid, stearic acid, oxalic acid, malonic acid,succinic acid, adipic acid, acrylic acid, methacrylic acid, oleic acid,maleic acid, chloroformic acid, chloroacetic acid, trifluoroacetic acid,cyclohexanecarboxylic acid, pivalic acid, benzoic acid, toluic acid,naphthoic acid, phthalic acid, cinnamic acid, nicotinic acid,thiophenecarboxylic acid, S-thioacetic acid, dithioacetic acid,S-thiobenzoic acid, dithiobenzoic acid, thiocarbonic acid,trithiocarbonic acid, xanthic acid, methanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, phenylphosphonic acid anddiphenylphosphinic acid. Considering handling, hydrochloric acid, nitricacid, sulfuric acid, p-toluenesulfonic acid and carboxylic acids arepreferred, and hydrochloric acid and acetic acid are more preferred.

An addition amount of the above acids is varied depending on the kind ofthe acid added, and it falls in a range of preferably 4 times mole ormore and 40 times mole or less, more preferably 4 times mole or more and10 times mole or less based on the compound (2). If they are added in 4times mole or more, the compound (2) can completely be converted to thesilanol. If the reaction is carried out in 4 times mole or less, anSi—ONa bond is likely to partially remain. On the other hand, if theacid is added too much, the resulting silanol falls in an instable stateand is likely to be condensed.

A temperature of this reaction falls, though depending on the kind ofthe compound (2), in a range of preferably −80 to 150° C., morepreferably 0 to 70° C. in order to sufficiently complete the reaction.If the reaction is carried out at a high temperature exceeding 150° C.,the resulting silanol falls in an instable state and is likely to becondensed. The reaction time is 0.1 to 8 hours, though this range of thereaction time shall not restrict the present invention since thereaction time is influenced by a concentration of the reaction solution,the reaction temperature and stirring in addition to a reactivity of thecompound (2).

As described above, the compound (1) can stably be obtained from thecompound (2) by carrying out the reaction, and if the product having ahigher purity is required, the object thereof can be achieved bycarrying out recrystallization, extraction and washing.

Next, a production process for polysiloxane using the compound (1) shallbe explained. The compound (1) has active silanol, and therefore variouspolysiloxanes can be obtained by reacting it with organosiliconcompounds having a hydrolytic group or silanol. For example, whenpolysiloxane is obtained only from the compound (1), the compound (1) isdissolved, if necessary, in a solvent, and a condensation catalyst isadded, if necessary, to carry out polycondensation reaction, wherebypolysiloxane represented by Formula (3) can be obtained.

The reaction can be allowed to effectively proceed to obtainpolysiloxane by adding a condensation catalyst in the reaction andcarrying out the reaction while drawing out water to the outside of thesystem.

In Formula (3), R³ is a group defined in the same manner as R¹ inFormula (1) of the item [1], and m is an integer of 2 to 1000.

In the present invention, silsesquioxane, silicone and silicon resinseach having an alkoxysilyl group, an acetoxysilyl group, an aminosilylgroup or a halosilyl group can be given as the examples of theorganosilicon compound having a hydrolytic group. To be specific, acompound having an incompletely condensed type structure represented byFormula (4) and a cyclic organosilicon compound represented by Formula(5) can be given as the examples of the organosilicon compound havingsilanol. Among the organosilicon compounds represented by Formula (4),the compounds in which a substituent represented by R⁴ is ethyl,isobutyl, cyclopentyl, cyclohexyl or isooctyl are commercially availableand can readily be obtained. The compounds which are not commerciallyavailable can be obtained as well by the methods shown in the non-patentdocuments 2 to 5 and the patent document 1.

The cyclic silsesquioxane represented by Formula (5) can be obtained bysubjecting trichlorosilane or trialkoxysilane to hydrolysis andpolycondensation by the publicly known technique shown in the non-patentdocument 2, 4 or 6.

In Formula (4) and Formula (5), R⁴ and R⁵ are groups defined in the samemanner as R¹ in Formula (1).

Further, silicone represented by Formula (8) can also be used as theorganosilicon compound having a hydrolytic group.

In Formula (8), R⁶ to R⁸ have the same meaning as that of R¹ in Formula(1), and R⁹ and R¹⁰ are a hydroxyl group, a hydrolytic group or a groupdefined in the same manner as R¹ in Formula (1). However, R⁹ and R¹⁰ arenot the group defined in the same manner as R¹ in Formula (1) at thesame time, and n is an integer of 2 to 500.

To be specific, capable of being given as the examples of the siliconehaving a hydroxyl group are DMS-S12 (product name, manufactured by AZmaxCo., Ltd.), DMS-S15 (product name, manufactured by AZmax Co., Ltd.),DMS-S21 (product name, manufactured by AZmax Co., Ltd.), DMS-S27(product name, manufactured by AZmax Co., Ltd.), DMS-S31 (product name,manufactured by AZmax Co., Ltd.), DMS-S32 (product name, manufactured byAZmax Co., Ltd.), DMS-S33 (product name, manufactured by AZmax Co.,Ltd.), DMS-S35 (product name, manufactured by AZmax Co., Ltd.), DMS-S38(product name, manufactured by AZmax Co., Ltd.), DMS-S42 (product name,manufactured by AZmax Co., Ltd.), DMS-S45 (product name, manufactured byAZmax Co., Ltd.), DMS-S51 (product name, manufactured by AZmax Co.,Ltd.), PSD-0332 (product name, manufactured by AZmax Co., Ltd.),PDS-1615 (product name, manufactured by AZmax Co., Ltd.), PDS-9931(product name, manufactured by AZmax Co., Ltd.) and FMS-9921 (productname, manufactured by AZmax Co., Ltd.).

DMS-X11 (product name, manufactured by AZmax Co., Ltd.) and DMS-X25(product name, manufactured by AZmax Co., Ltd.) can be given as theexamples of silicone having an alkoxysilyl group as a hydrolytic group.Capable of being given as the examples of silicone having a chlorosilylgroup as a hydrolytic group are DMS-K05 (product name, manufactured byAZmax Co., Ltd.), DMS-K13 (product name, manufactured by AZmax Co.,Ltd.) and DMS-K26 (product name, manufactured by AZmax Co., Ltd.).DMS-D33 (product name, manufactured by AZmax Co., Ltd.) can be given asthe example of silicone having an acetoxysilyl group as a hydrolyticgroup. DMS-N05 (product name, manufactured by AZmax Co., Ltd.) can begiven as the example of silicone having an aminosilyl group as ahydrolytic group. All the above compounds are commercially availablefrom AZmax Co., Ltd. and can easily be obtained.

Also, the compounds having a hydroxyl group at one end which are notcommercially available can be obtained as well by a method disclosed inthe patent document 2 by Nakano et al., that is, by subjecting cyclicpolysiloxane to anionic polymerization using triorganosilanol as aninitiator under the presence of 0.12 to 2.0 mole % of a lithium basecatalyst. Further, the compounds having hydroxyl groups at both ends canbe obtained by a method disclosed in the patent document 3 by Akutsu etal., that is, by subjecting cyclic polysiloxane to anionicpolymerization in a polar solvent having no active hydrogen using wateras an initiator under the presence of 0.12 to 10 mole % of a lithiumbase catalyst based on the initiator.

In producing the polysiloxane of the present invention, a solvent is notnecessarily required, but it can be used in the present invention aslong as it does not hinder the progress of the reaction. Capable ofbeing specifically given as the examples thereof are, for example,aromatic hydrocarbons such as benzene, toluene and xylene, aliphatichydrocarbons such hexane and heptane, alcohols such as methanol,ethanol, n-propanol and iso-propanol, ethers such as dimethyl ether,diethyl ether, tetrahydrofuran and 1,4-dioxane, acetates such as methylacetate, ethyl acetate and butyl acetate, amides such asN,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone,ketones such as acetone, 2-butanone and methyl iso-butyl ketone,acetonitrile and dimethylsulfoxide. Among them, tetrahydrofuran,acetates, dimethylformamide and toluene are preferred. In the presentinvention, an addition amount thereof shall not be restricted, and it is0.01 to 100 parts by weight per one part by weight of the compound (1).

Usually known polycondensation catalysts for silanol can be used as thepolycondensation catalyst used in the present invention. Capable ofbeing given as the examples thereof are, for example, alkaline compoundssuch as sodium hydroxide and potassium hydroxide, amines such asethylenediamine, N,N,N′,N′-tetramethylethylenediamine,diethylenetriamine, triethylamine, tributylamine, dimethylaniline,1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undeca-7-ene and2,5-diazabicyclo[2.2.1]heptane, quaternary ammonium salts such astetramethylammonium acetate, tetramethylammonium hydroxide and ammoniumperchrorate, carbodiimides such as dicyclohexylcarbodiimide and1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, organic titaniumcompounds such as tetraisopropyl titanate, tetra-n-butyl titanate,titanium diacetylacetonate and titanium diisopropyl-bisacetylacetonate,organic tin compounds such as dibutyltin diacetate, dibutyltin dioctate,dibutyltin dilaurate and dibutyltin maleate, acid compounds such ashydrochloric acid, trichloroacetic acid, p-toluenesulfonic acid,phosphoric acid, acetic acid and acetic anhydride, a reaction product ofn-hexylamine and 2-ethylhexanoic acid and a reaction product oftetramethylguanidine and 2-ethylhexanoic acid. An addition amount of theabove polycondensation catalysts falls, though varied depending on thekind thereof, in a range of usually 0.01 to 100 parts by weight per 100parts by weight of the compound (1).

The polysiloxane thus obtained which is soluble in a solvent makes itpossible to provide a flat, even and transparent thin film by spincoating in the form of a solution. Accordingly, it is useful as anelectronic material, an optical material, a coating material and asealing material, and it is expected to be applied to them.

EXAMPLES

The present invention shall be explained below in details with referenceto examples, but the present invention shall not be restricted by theseexamples. In chemical formulas in the following examples, Ph representsphenyl; Me represents methyl; and TMS represents trimethylsilyl. Theaverage molecular weight is a value measured by gel permeationchromatography (GPC) using tetrahydrofuran as a solvent and calculatedfrom a calibration curve prepared using standard polystyrene. Thenuclear magnetic resonance spectrum was measured using tetramethylsilaneas an internal standard substance.

Example 1

<Synthesis of Organosilicon Compound>

A reactor of 50 liter equipped with a reflux condenser, a thermometerand a stirrer was charged with phenyltrimethoxysilane (6.54 kg),2-propanol (26.3 liter), purified water (0.66 kg) and sodium hydroxide(0.88 kg) and sealed with nitrogen. The reactor was heated while heatingto carry out reaction for 5 hours in a refluxing state. After finishingthe reaction, the reactor was left standing at room temperature for 15hours, and then the supernatant was removed by decantation. 2-Propanol(9.87 kg) was added thereto and stirred, and then the solution wasfiltrated by means of a pressure filter equipped with a filter paper(No. 2) manufactured by Advantech Co., Ltd. to obtain a white solidmatter. Then, the white solid matter obtained was transferred into a vatmade of stainless steal which was lined with a polytetrafluoroethylenesheet, and it was dried at an inside temperature of 80° C. and apressure of 6.7×10⁻⁴ MPa for 24 hours by means of a vacuum dryer toobtain 2.22 kg of a white solid matter of a powder form.

<Confirmation of the Structure of the White Solid Matter of a PowderForm>

A reaction vessel having a content volume of 50 ml equipped with adropping funnel and a thermometer was charged with the white solidmatter of a powder form (1.2 g) obtained above, THF (15 g) andtriethylamine (1.4 g), and the vessel was sealed with dry nitrogen.Chlorotrimethylsilane (2.5 g) was dropwise added thereto from thedropping funnel under stirring by means of a magnetic stirrer. Aftercontinuing to stir the solution at 25° C. for 4 hours, ion-exchangedwater (10 g) was added thereto and stirred for 5 minutes, and thentoluene (15 g) was added and stirred for 10 minutes. The reactionmixture thus obtained was separated into an organic layer and an aqueouslayer, and the organic layer was repeatedly washed with ion-exchangedwater to confirm that the washing solution was neutral. The organiclayer was dried on anhydrous magnesium sulfate and concentrated underreduced pressure to obtain 1.2 g of a white solid matter. The whitesolid matter thus obtained was analyzed by means of GPC, ¹H-NMR and²⁹Si-NMR to carry out structural analysis. The results thereof are shownbelow.

GPC:

Number average molecular weight (Mn)=950

Weight average molecular weight (Mw)=990

¹H-NMR (CDCl₃):

δ (ppm)=0.05[s, 36H, —Si(CH₃)₃], 7.09 to 7.50[m, 40H, —SiC₆H₅]

²⁹Si-NMR (CDCl₃):

δ (ppm)=−78.95, −76.12[s, 1:1, —SiC₆H₅], 10.62[s, —Si (CH₃)₃]

The analytical results described above supported a structure of Formula(a). Accordingly, it is judged that the compound beforetrimethylsilylated has a chemical structure represented by Formula (9).

Example 2

<Synthesis of Organosilicon Compound having Silanol>

A reaction vessel of 200 ml equipped with a dropping funnel, athermometer and a rotator was charged with the organosilicon compound(9) (10 g) obtained in Example 1 and butyl acetate (100 ml), and thevessel was sealed with nitrogen and cooled on an ice bath. Acetic acid(3.0 g) was dropwise added under stirring by means of a magnetic stirrerwhile maintaining the solution temperature at 10° C. or lower. Afterfinishing dropwise adding, stirring was continued at 0° C. for 2 hours,and then ion-exchanged water (20 g) was dropwise added. After finishingdropwise adding, stirring was continued for 10 minutes, and then thesolution was transferred into a separating funnel and separated into anorganic layer and an aqueous layer. The organic layer thus obtained wasneutralized by a saturated sodium hydrogencarbonate aqueous solution,and then it was washed twice with saturated brine and twice withion-exchanged water. The organic layer was dried on anhydrous magnesiumsulfate, filtered and then concentrated (oil bath temperature: 45° C.)under vacuum by means of a rotary evaporator. Next, acetone (24.0 g) wasadded to the resulting residue, and the mixture was stirred at roomtemperature for 10 minutes. Then, the solution was filtrated underreduced pressure through a membrane filter having a pore diameter of 3μm to obtain a white solid matter. The white solid matter thus obtainedwas dried at room temperature under vacuum to result in obtaining 10.0 gof a white solid matter of a powder form.

The white solid matter of a powder form thus obtained was subjected tostructural analysis by means of an infrared absorption spectrum (IR),²⁹Si-NMR and GPC. The results thereof are shown below.

IR (KBr):

n=3300 cm⁻¹ [Si—OH]

950 cm⁻¹ [Si—OH]

²⁹Si-NMR (THF):

δ (ppm)=−69.32[s, —PhSi(OH)O_(2/2)], −79.45[s, —PhSiO_(3/2)]

GPC:

Number average molecular weight (Mn)=760

Weight average molecular weight (Mw)=780

The data described above indicated that the white solid matter of apowder form has a structure of Formula (10).

Example 3

<Synthesis of Organosilicon Compound having Silanol>

A reaction vessel having a volume content of 100 ml equipped with adropping funnel and a thermometer was charged with the organosiliconcompound (9) (6 g) obtained in Example 1 and tetrahydrofuran (50 ml),and the vessel was sealed with dry nitrogen. Then, acetic acid (2.4 g)was dropwise added in about 10 seconds under stirring while maintainingthe solution temperature at 22 to 27° C. After finishing dropwiseadding, stirring was continued at room temperature for one hour, andthen ion-exchanged water (20 g) was dropwise added thereto. Afterfinishing dropwise adding, stirring was continued for 10 minutes, andthen the solution was transferred into a separating funnel to separatean organic layer from an aqueous layer. The organic layer thus obtainedwas washed once with a saturated sodium hydrogencarbonate aqueoussolution, and then it was repeatedly washed with water to confirm thatthe washing solution was neutral. Next, the organic layer was dried onanhydrous magnesium sulfate and then concentrated under vacuum to obtain5.3 g of a white solid matter of a powder form.

The white solid matter of a powder form thus obtained was analyzed inthe same manner as in Example 2. As a result thereof, the same spectraas in Example 2 were obtained, and it was confirmed that the above whitesolid matter of a powder form had the same structure as that of Formula(10).

Example 4

<Synthesis of Polysiloxane>

A reaction vessel of 200 ml equipped with a reflux condenser and arotator was charged with the organosilicon compound (10) (5 g) obtainedin Example 2 and toluene (120 ml). A molar ratio 1:2 mixed solution ofn-hexylamine/2-ethylhexanoic acid (0.05g) was added thereto, and thevessel was sealed with nitrogen. Then, the vessel was heated on an oilbath while stirring by means of a magnetic stirrer. After the reactionsolution reached a refluxing state, the reaction was continued for 16.5hours. Thereafter, the solution was cooled down to room temperature andfiltered, and then it was concentrated under reduced pressure to obtaina white solid matter.

The white solid matter thus obtained was analyzed by GPC to find thatthe number average molecular weight (Mn) was 1500 and that the weightaverage molecular weight (Mw) was 3300. As a result thereof, it wasconfirmed that the white solid matter thus obtained was apolycondensation product of the organosilicon compound (10).

Example 5

<Synthesis of Polysiloxane>

A reaction vessel of 100 ml equipped with a reflux condenser and arotator was charged with the organosilicon compound (10) (2.14 g)obtained in Example 2, dimethylsulfoxide (30 ml) andN,N-dicyclohexylcarbodiimide (1.24 g) and sealed with nitrogen. Then,the vessel was heated on an oil bath while stirring by means of amagnetic stirrer. After the reaction solution reached 125° C., thereaction was continued for 43 hours and, then the solution was cooleddown to room temperature. The solution was repeatedly washed three timeswith water, dried on anhydrous magnesium sulfate and filtered, and thenit was concentrated under reduced pressure to obtain 0.6 g of a whitesolid matter.

The white solid matter thus obtained was measured for a molecular weightby GPC to find that the number average molecular weight (Mn) was 3000and that the weight average molecular weight (Mw) was 3800. As a resultthereof, it was confirmed that the white solid matter thus obtained wasa polycondensation product of the organosilicon compound (10).

Example 6

<Synthesis of Polysiloxane>

A reaction vessel of 200 ml equipped with a reflux condenser, a rotatorand a deanstark filled with molecular sieve 3A is charged with theorganosilicon compound (10) (5 g) obtained in Example 2 and toluene (120ml). p-Toluenesulfonic acid monohydrate (0.05 g) is added thereto, andthe vessel is sealed with nitrogen. Then, the vessel is heated on an oilbath while stirring by means of a magnetic stirrer. After the reactionsolution reach a refluxing state, the reaction is continued for 24hours. Thereafter, the solution is cooled down to room temperature andwashed once with a saturated sodium hydrogencarbonate aqueous solution,and then it is washed three times with ion-exchanged water to confirmthat the washing solution is neutral. The organic layer obtained isdried on anhydrous magnesium sulfate, and then it is filtered andconcentrated under vacuum to obtain a white solid matter.

The above white solid matter is measured for a molecular weight by GPCto find that the number average molecular weight (Mn) is 30000 and thatthe weight average molecular weight (Mw) is 100000 and, it is confirmedthat the above white solid matter is a polycondensation product of theorganosilicon compound (10).

Example 7

<Synthesis of Polysiloxane>

A reaction vessel of 50 ml equipped with a reflux condenser, a rotatorand a thermometer was charged with the organosilicon compound (10) (1.00g) obtained in Example 2, dimethylsiloxane having chlorine at both endsas silicone having a hydrolytic group, DMS-K05 (0.85 g) manufactured byAZmax Co., Ltd. and tetrahydrofuran (20 g), and the vessel was sealedwith nitrogen. Reaction was carried out at room temperature for 1.5 hourwhile stirring by means of a magnetic stirrer, and then triethylamine(0.40 g) was charged thereinto. Then, the vessel was heated on an oilbath to carry out refluxing for 5 hours. The solution was cooled down toroom temperature and then washed once with 1N hydrochloric acid andthree times with ion-exchanged water. The organic layer was dried onanhydrous magnesium sulfate, filtered and then concentrated under vacuumto obtain 0.6 g of a viscous liquid.

The viscous liquid thus obtained was measured for a molecular weight byGPC to find that the number average molecular weight (Mn) was 3000 andthat the weight average molecular weight (Mw) was 3800. As a resultthereof, it was confirmed that the viscous liquid obtained waspolysiloxane comprising the organosilicon compound (10) anddimethylsilicone.

1. An organosilicon compound represented by Formula (1):

wherein each R¹ is a group selected independently from hydrogen, alkylhaving 1 to 45 carbon atoms, substituted or unsubstituted aryl, andarylalkyl; in which in the alkyl optional hydrogen may be replaced byfluorine and optional —CH₂— may be replaced by —O—, —CH═CH—,cycloalkylene, or cycloalkenylene, and arylalkyl is constituted ofalkylene in which optional hydrogen may be replaced by fluorine andoptional —CH₂— may be replaced by —O—, —CH═CH— or cycloalkylene, andsubstituted or unsubstituted aryl.
 2. The organosilicon compoundaccording to claim 1, wherein each R¹ is a group selected independentlyfrom hydrogen and alkyl having 1 to 30 carbon atoms, in which in thealkyl optional hydrogen may be replaced by fluorine and optional —CH₂—may be replaced by —O— or cycloalkylene.
 3. The organosilicon compoundaccording to claim 1, wherein each R¹ is a group selected independentlyfrom hydrogen, alkenyl having 2 to 20 carbon atoms and alkyl having 1 to20 carbon atoms; in which in the alkenyl optional hydrogen may bereplaced by fluorine and optional —CH₂— may be replaced by —O— orcycloalkylene, and in the alkyl optional hydrogen may be replaced byfluorine and at least one —CH₂— is replaced by cycloalkenylene.
 4. Theorganosilicon compound according to claim 1, wherein each R¹ is a groupselected independently from hydrogen, phenyl and naphthyl; in which inthe phenyl optional hydrogen may be replaced by halogen or alkyl having1 to 10 carbon atoms, in the alkyl which is a substituent of the phenyloptional hydrogen may be replaced by fluorine and optional —CH₂— may bereplaced by —O—, —CH═CH—, cycloalkylene or phenylene; and when thephenyl or the naphthyl has plural substituents, the substituents may bethe same group or different groups.
 5. The organosilicon compoundaccording to claim 1, wherein each R¹ is a group selected independentlyfrom hydrogen and phenylalkyl constituted of phenyl and alkylene having1 to 12 carbon atoms; in which in the phenyl optional hydrogen may bereplaced by halogen or alkyl having 1 to 10 carbon atoms, in the alkylwhich is a substituent of the phenyl optional hydrogen may be replacedby fluorine and optional —CH₂— may be replaced by —O—, —CH═CH—,cycloalkylene or phenylene, and in the alkylene optional hydrogen may bereplaced by fluorine and optional —CH₂— may be replaced by —O— orcycloalkylene; and when the phenyl has plural substituents, thesubstituents may be the same group or different groups.
 6. Theorganosilicon compound according to claim 1, wherein each R¹ is a groupselected independently from hydrogen and phenylalkenyl constituted ofphenyl and alkenylene having 2 to 12 carbon atoms; in which in thephenyl optional hydrogen may be replaced by halogen or alkyl having 1 to10 carbon atoms, in the alkyl which is a substituent of the phenyloptional hydrogen may be replaced by fluorine and optional —CH₂— may bereplaced by —O—, —CH═CH—, cycloalkylene or phenylene, and in thealkenylene optional hydrogen may be replaced by fluorine and optional—CH₂— may be replaced by —O— or cycloalkylene; and when the phenyl hasplural substituents, the substituents may be the same group or differentgroups.
 7. The organosilicon compound according to claim 1, wherein eachR¹ is a group selected independently from hydrogen, alkyl having 1 to 8carbon atoms, phenyl, phenylalkyl constituted of phenyl and alkylenehaving 1 to 8 carbon atoms, and naphthyl; in which in the alkyl optionalhydrogen may be replaced by fluorine and optional —CH₂— may be replacedby —O—, —CH═CH—, cycloalkylene or cycloalkenylene, in the phenyloptional hydrogen may be replaced by halogen, methyl or methoxy, in thephenyl of phenylalkyl optional hydrogen may be replaced by fluorine,alkyl having 1 to 4 carbon atoms, vinyl or methoxy, and in the alkyleneof phenylalkyl optional —CH₂— may be replaced by —O—, —CH═CH— orcycloalkylene; and when the phenyl has plural substituents, thesubstituents may be the same group or different groups.
 8. Theorganosilicon compound according to claim 1, wherein all of R¹'s are thesame group selected from hydrogen, alkyl having 1 to 8 carbon atoms,phenyl, phenylalkyl constituted of phenyl and alkylene having 1 to 8carbon atoms, and naphthyl; in which in the alkyl optional hydrogen maybe replaced by fluorine and optional —CH₂— may be replaced by —O—,—CH═CH—, cycloalkylene or cycloalkenylene, in the phenyl optionalhydrogen may be replaced by halogen, methyl or methoxy, in the phenyl ofphenylalkyl optional hydrogen may be replaced by fluorine, alkyl having1 to 4 carbon atoms, vinyl or methoxy, and in the alkylene ofphenylalkyl optional —CH₂— may be replaced by —O—, —CH═CH— orcycloalkylene; and when the phenyl has plural substituents, thesubstituents may be the same group or different groups.
 9. Theorganosilicon compound according to claim 1, wherein all of R¹'s are thesame group selected from hydrogen, phenyl, phenylalkyl constituted ofphenyl and alkylene having 1 to 8 carbon atoms, and naphthyl; in whichin the phenyl optional hydrogen may be replaced by halogen, methyl ormethoxy, in the phenyl of phenylalkyl optional hydrogen may be replacedby fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy, and inthe alkylene of phenylalkyl optional —CH₂— may be replaced by —O—,—CH═CH— or cycloalkylene; and when the phenyl has plural substituents,the substituents may be the same group or different groups.
 10. Theorganosilicon compound according to claim 1, wherein all of R¹'s arephenyl.
 11. A production process for the organosilicon compound definedin claim 1, characterized by using an organosilicon compound representedby Formula (2):

wherein R² is the same as that of R¹ in Formula (1) defined in claim 1,and M is a monovalent alkaline metal atom.
 12. A production process forthe organosilicon compound defined in claim 1, characterized by reactingthe organosilicon compound represented by Formula (2) with a protondonor.
 13. A production process for the organosilicon compound definedin claim 1, characterized by reacting the organosilicon compoundrepresented by Formula (2) with an inorganic acid.
 14. A productionprocess for the organosilicon compound defined in claim 1, characterizedby reacting the organosilicon compound represented by Formula (2) withan organic acid.
 15. Polysiloxane represented by Formula (3):

wherein R³ has the same meaning as that of R¹ in Formula (1) defined inclaim 1, and m is an integer of 2 to
 1000. 16. The polysiloxaneaccording to claim 15, wherein m is an integer of 2 to
 500. 17. Thepolysiloxane according to claim 15, wherein m is an integer of 2 to 50.18. Polysiloxane obtained by subjecting the organosilicon compoundaccording to claim 1 to polycondensation reaction.
 19. Polysiloxaneobtained by reacting the organosilicon compound according to claim 1with an organosilicon compound having a hydrolytic group. 20.Polysiloxane obtained by reacting the organosilicon compound accordingto claim 1 with an organosilicon compound having silanol.
 21. Thepolysiloxane according to claim 19, wherein the hydrolytic group is analkoxysilyl group.
 22. The polysiloxane according to claim 19, whereinthe hydrolytic group is an acetoxysilyl group.
 23. The polysiloxaneaccording to claim 19, wherein the hydrolytic group is a halosilylgroup.
 24. The polysiloxane according to claim 19, wherein thehydrolytic group is an aminosilyl group.
 25. A production process forpolysiloxane, characterized by subjecting the organosilicon compoundaccording to claim 1 to polycondensation reaction.
 26. A productionprocess for polysiloxane, characterized by reacting the organosiliconcompound according to claim 1 with an organosilicon compound having ahydrolytic group.
 27. A production process for polysiloxane,characterized by reacting the organosilicon compound according to claim1 with an organosilicon compound having silanol.
 28. The productionprocess for polysiloxane according to claim 26, wherein the hydrolyticgroup is an alkoxysilyl group.
 29. The production process forpolysiloxane according to claim 26, wherein the hydrolytic group is anacetoxysilyl group.
 30. The production process for polysiloxaneaccording to claim 26, wherein the hydrolytic group is a halosilylgroup.
 31. The production process for polysiloxane according to claim26, wherein the hydrolytic group is an aminosilyl group.